JP2002114946A - Coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating composition, which contains a microcapsule where a proliferation inhibitor against microbes as an active ingredient is well microcapsulated, and consequently can produce fine effects even when a small amount of the proliferation inhibitor against microbes is used, achieve much improvement in persistency of the effects and in sustained release property and ensure stable qualities. SOLUTION: A microcapsule containing a proliferation inhibitor against microbes is incorporated into a coating composition, where the proliferation inhibitor against microbes is microcapsulated with a membrane formed by a reaction of a polyisocyanate component having an amine equivalent of 140-300 with an active hydrogen group-containing component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a coating composition, and more particularly to a coating composition containing microcapsules containing a microbial growth inhibitor.

[0002]

2. Description of the Related Art Conventionally, various coating compositions have been formulated with a microbial growth inhibitor which exhibits antibacterial properties, antifungal properties, antialgal properties, etc. in order to suppress the growth of harmful microorganisms. . Such a microbial growth inhibitor has many unstable compounds and is easily decomposed.For example, a metal salt is added to a compound to be an active ingredient, or a compound to be an active ingredient is included. By stabilizing, it is attempted to improve the sustainability of the efficacy, thereby improving the stability in the coating composition and the persistence of the efficacy after coating.

[0003] In addition, various proposals have been made to improve the sustainability of the efficacy and the sustained release by microencapsulating a compound as an active ingredient.
JP-A-64-70505 proposes to microencapsulate a fungicide with a polyisocyanate.

[0004]

However, for example, a compound having skin irritation, even if it is a metal salt or clathrate, may hinder the working environment when it is incorporated into a coating composition.

[0005] On the other hand, if microencapsulation is used, the working environment can be improved.
Improvement in sustainability of efficacy and sustained release even when microencapsulation is carried out using a polyisocyanate monomer or a derivative of a polyisocyanate monomer usually used as a raw material of polyurethane as described in JP 70505 It is difficult to achieve sufficient.

Further, in recent years, from the viewpoint of protecting the global environment, the use of organic solvent-based coating compositions has been restricted, and instead, aqueous coating compositions have been variously developed. In particular, when a microbial growth inhibitor is blended with such an aqueous paint composition, crystallization occurs during the blending, and a stable paint composition cannot be obtained. In some cases.

The present invention has been made in view of such circumstances, and it is an object of the present invention that a microbial growth inhibitor as an active ingredient is satisfactorily encapsulated in microcapsules. Even when the amount used is small, a coating composition that exhibits excellent efficacy, can sufficiently improve the sustainability of the efficacy and sustained release properties, and can ensure stable quality. To provide.

[0008]

In order to achieve the above-mentioned object, the present invention provides (1) a method for producing a microorganism growth inhibitor by reacting a polyisocyanate component having an amine equivalent of 140 to 300 with an active hydrogen group-containing component. A coating composition comprising microbial growth inhibitor-containing microcapsules microencapsulated by a film to be formed, (2) trifunctional or more functional in a polyisocyanate component having an amine equivalent of 140 to 300. The coating composition according to the above (1), which contains a polyisocyanate compound. (3) The active hydrogen group-containing component is water and / or a polyamine having 2 to 12 carbon atoms. The coating composition according to the above (1) or (2), wherein the microorganism growth inhibitor is a thiophene compound or an isothiazoline compound. And (5) an aqueous coating composition according to any one of (1) to (3), wherein the coating composition comprises at least one active ingredient selected from the group consisting of: The coating composition according to any one of the above (1) to (4), characterized in that it is the coating composition of (1).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The coating composition of the present invention contains microcapsules containing a microbial growth inhibitor. First,
The microcapsule containing a microorganism growth inhibitor used in the present invention will be described in detail.

In the microcapsules containing a microbial growth inhibitor of the present invention, a microbial growth inhibitor is encapsulated as an active ingredient. Microbial growth inhibitors are compounds that exhibit antibacterial, antifungal and antialgal properties, and various industrial germicides such as bactericides, antibacterial agents, antifungal agents, preservatives, and antialgal agents. included.

As such a microorganism growth inhibitor, for example, thiophene compounds such as 3,3,4,4-tetrachlorotetrahydrothiophen-1,1-dioxide, for example, 2-n-octyl-4-isothiazoline −
3-one, 2-ethyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 5-
Chloro-2-t-octyl-4-isothiazoline-3-
On, 5-chloro-2-ethyl-4-isothiazoline-
3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-
4-isothiazolin-3-one, 4,5-dichloro-2
-Cyclohexyl-4-isothiazolin-3-one, 2
Isothiazoline-based compounds such as -methyl-4,5-trimethylene-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, n-butyl-benzoisothiazolin-3-one, for example, 3-iodo- 2-
Propynyl-butyl-carbamate, diiodomethyl-
Organic iodine compounds such as p-toluylsulfone and p-chlorophenyl-3-iodopropargyl formal, for example, 4,5-dichloro-1,2-dithiol-
Dithiol compounds such as 3-one, for example, thiocarbamate compounds such as tetramethylthiuram disulfide, for example, nitrile compounds such as 2,4,5,6-tetrachloroisophthalonitrile, for example, N- (fluorodichloro Methylthio) -phthalimide, N- (fluorodichloromethylthio) -N, N'-dimethyl-N
Haloalkylthio compounds such as -phenyl-sulfamide, for example, 2,3,5,6-tetrachloro-4-
Pidyline-based compounds such as (methylsulfonyl) pyridine, for example, pyrithione-based compounds such as zinc pyrithione and sodium pyrithione, for example, benzothiazole-based compounds such as 2- (4-thiocyanomethylthio) benzothiazole, for example, 2-methylthio-4 Triazine compounds such as -t-butylamino-6-cyclopropylamino-s-triazine, for example, methyl-2-benzimidazole carbamate, 2- (4-thiazolyl)
-Imidazole compounds such as benzimidazole, for example, 1-[[2- (2,4-dichlorophenyl)-
1,3-dioxan-2-yl] methyl] -1H-1,
2,4-triazole, (±) -α [2- (4-chlorophenyl) ethyl] -α- (1,1-dimethylethyl)
-1H-1,2,4-triazole- (1) -ethanol (tepconazole), (±) -1- [2- (2,4-
Triazole-based compounds such as dichlorophenyl) -4-propyl-1,3-dioxan-2-ylmethyl] -1H-1,2,4-triazole, for example, 3-benzo [b] thien-2-yl-5,6- Dihydro-1,4
Oxathiazine-based compounds such as 2-oxathiazine-4-oxide, for example, 2,2-dibromo-2-nitroethanol, 2-bromo-2-nitropropane 1,3-
Alcohol compounds such as diols, for example, 3-
Amide compounds such as (3,4-dichlorophenyl) -1,1-dimethylurea urea compound and 2,2-dibromo-3-nitrilopropanamide are exemplified.

These microorganism growth inhibitors may be used alone or in combination of two or more. Preferably,
Thiophene-based compounds, isothiazoline-based compounds, and organic iodine-based compounds are exemplified.

The microcapsule containing the microbial growth inhibitor of the present invention comprises an oil phase containing a microbial growth inhibitor and a polyisocyanate component having an amine equivalent of 140 to 300, and an aqueous phase containing an active hydrogen group-containing component. It can be obtained by blending, dispersing and interfacial polymerization.

The oil phase may be prepared, for example, by mixing an organic solvent with a microbial growth inhibitor and a polyisocyanate component having an amine equivalent of 140 to 300.

As the organic solvent, for example, a solvent having a boiling point of 100
An organic solvent having a high boiling point of from 500 to 500C, preferably from 150 to 450C is preferably used. By using a high-boiling organic solvent, the persistence of the efficacy of the microencapsulated microbial growth inhibitor can be improved. Such high-boiling organic solvents include, for example, alkylbenzenes, alkylnaphthalenes, alkylphenols, phenylxylylethane, etc., and more specifically, various commercially available high-boiling organic solvents obtained from petroleum fractions. Solvent, for example, Sartrex 48 (high-boiling aromatic solvent, distillation range: 254 to 386 ° C, Mobil Petroleum Co., Ltd.
Alkene L (alkylbenzene, distillation range 285)
To 309 ° C, manufactured by Nippon Petrochemical Co., Ltd.), Solvesso 10
0 (alkylbenzene, distillation range: 164 to 180 ° C., manufactured by Exxon Chemical Co., Ltd.), Solvesso 150 (alkylbenzene, distillation range: 188 to 210 ° C., manufactured by Exxon Chemical Co., Ltd.), Solvesso 200 (alkylbenzene, distillation range: 226 to 286 ° C.) Exxon Chemical Co., Ltd.), K
MC-113 (diisopropyl naphthalene, boiling point 300
° C, manufactured by Kureha Chemical Industry Co., Ltd.), SAS296 (phenylxylylethane, distillation range: 290-305 ° C, manufactured by Nippon Petrochemical Co., Ltd.), Allosizer 202 (ethyl biphenyl, boiling point: 286 ° C, manufactured by Nippon Steel Chemical Co., Ltd.) ).

As other organic solvents, for example,
Aliphatic hydrocarbons such as hexane, cyclohexane, octane and decane, for example, aromatic hydrocarbons such as benzene, toluene and xylene, for example, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate Esters such as ethylene glycol monobutyl ether acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethers such as 1,4-dioxane and tetrahydrofuran; for example, hexanol, octanol, benzyl alcohol, furfuryl Alcohols such as alcohols, for example, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol Polyol, tripropylene glycol, polypropylene glycol, 1,4-butanediol, 1,5-pentanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol Glycols such as propylene glycol monomethyl ether, for example, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,1,1-trichloroethane, chlorobenzene, dichlorobenzene, for example, N-methylpyrrolidone, N, N- Examples thereof include nitrogen-containing compounds such as dimethylaniline, pyridine, acetonitrile, and dimethylformamide. These organic solvents may be used alone or in combination of two or more.

Examples of the polyisocyanate component having an amine equivalent of 140 to 300 include a modified polyisocyanate obtained by reacting a polyisocyanate monomer and / or a derivative of the polyisocyanate monomer with a compound having an active hydrogen group, and a modified polyisocyanate. A combination of a polyisocyanate and a polyisocyanate monomer and / or a derivative of a polyisocyanate monomer may be used. The amine equivalent is defined as (molecular weight of polyisocyanate compound / number of isocyanate groups), and in the present invention, the amine equivalent is more preferably in the range of 140 to 250.

The polyisocyanate monomer can be used without any particular limitation as long as it is a polyisocyanate monomer usually used as a raw material for polyurethane. Examples of such polyisocyanate monomers include aliphatic diisocyanates such as hexamethylene diisocyanate, for example, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3 -Or an alicyclic diisocyanate such as 1,4-bis (isocyanatomethyl) cyclohexane or a mixture thereof, for example, 1,3- or 1,4
-Xylylene diisocyanate or a mixture thereof,
1,3- or 1,4-bis (1-isocyanate-1
Araliphatic diisocyanates such as -methylethyl) benzene or a mixture thereof, for example, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, and an aromatic diisocyanate such as diphenylmethane-4,4'-diisocyanate; Can be

Examples of the polyisocyanate monomer derivatives include dimers and trimers of the above-mentioned polyisocyanate monomers, and polynuclear compounds such as polymethylene polyphenyl polyisocyanate (crude MDI and polymeric MDI). For example, a biuret form, an allophanate form, an oxadiazinetrione form, and the like, which are respectively formed by a reaction of the above-described polyisocyanate monomer with urea, urethane, carbon dioxide, or the like, may be mentioned.

The active hydrogen group-containing compound is a compound capable of reacting with an isocyanate group, for example, having an active hydrogen group such as a hydroxyl group or an amino group. Can be used without any particular limitation. Such active hydrogen group-containing compounds include, for example, low molecular polyols, low molecular polyamines and macropolyols.

Examples of the low molecular polyol include ethylene glycol, propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,6-hexanediol, neopentyl glycol, and alkane. (C7-C22) diol, diethylene glycol, triethylene glycol,
Dipropylene glycol, cyclohexane dimethanol, alkane-1,2-diol (C17 to C20),
Hydrogenated bisphenol A, 1,4-dihydroxy-2-
Low molecular weight diols such as butene, 2,6-dimethyl-1-octene-3,8-diol, bishydroxyethoxybenzene, xylene glycol, bishydroxyethylene terephthalate, for example, glycerin, 2-methyl-
2-hydroxymethyl-1,3-propanediol,
2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, 1,1,1-tris (hydroxymethyl) propane, 2,2-bis (hydroxymethyl) -3-butanol, and others And low molecular weight triols such as aliphatic triols (C8-24).

Examples of the low-molecular polyamine include ethylenediamine, propylenediamine, 1,4-butanediamine, hexamethylenediamine, octamethylenediamine, hydrazine, 1,2-diaminoethane, and 1,2-diamine.
Low molecular weight diamines such as diaminopropane, 1,3-diaminopentane, diaminotoluene, bis- (4-aminophenyl) methane, bis- (4-amino-3-chlorophenyl) methane, and diethylenetriamine, triethylenetetramine, tetraethylene Low-molecular amines having three or more amino groups, such as ethylenepentamine, pentaethylenehexamine, and 2,2′-diaminodiethylamine, may be mentioned.

The macropolyol is obtained, for example, by the addition reaction of the above-mentioned low-molecular polyol and low-molecular polyamine with an alkylene oxide such as ethylene oxide or propylene oxide, or by ring-opening polymerization of tetrahydrofuran or the like. Oxyalkylene polyols, for example, one or more low molecular polyols, and for example, oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxylate Propane, 3-methyl-3-ethylglutaric acid, azelaic acid, sebacic acid, and other aliphatic dicarboxylic acids (C11
To C13), heptic acid, and acid anhydrides derived from these carboxylic acids, for example, oxalic anhydride, succinic anhydride, 2-alkyl (C12-C18) succinic anhydride,
Furthermore, acid halides derived from these carboxylic acids, for example, obtained by reaction with dichloride oxalic acid, dichloride adipic acid, dichloride sebacate, or using a low molecular polyol as an initiator, ε
-Caprolactone, polyester polyols obtained by ring-opening polymerization of lactones such as γ-valerolactone, and polycarbonate polyols obtained by ring-opening polymerization of carbonates such as ethylene carbonate using a low molecular weight polyol as an initiator, and natural products such as castor oil. Examples include polyolefin polyols such as oil and fat polyols, polybutadiene polyols, and polyisoprene polyols.

These low molecular polyols, low molecular polyamines and macropolyols may be used alone.
Also, two or more kinds may be used in combination. Preferably, a macro polyol and a low molecular polyol are used. As the macro polyol, a polyoxyalkylene polyol and a polyester polyol are preferable. Above all,
Among the polyoxyalkylene polyols, polypropylene glycol (including those having a polyoxyethylene unit) and polytetramethylene ether glycol are preferred, and among the polyester polyols,
Polyethylene adipate, polypropylene adipate,
Polyethylene propylene adipate, polybutylene adipate and polycaprolactone diol are preferred.

The modified polyisocyanate is obtained by mixing the above-mentioned polyisocyanate monomer and / or the derivative of the polyisocyanate monomer with the above-mentioned active hydrogen group-containing compound in an equivalent ratio of isocyanate groups to active hydrogen groups (isocyanate group / active hydrogen group). At least in a ratio exceeding 1 under known urethanization conditions. The amine equivalent of the modified polyisocyanate thus obtained is 100 to 5000, and more preferably 200 to 2000.
It is preferable that

The polyisocyanate component having an amine equivalent of 140 to 300 may be used, for example, when the above-mentioned modified polyisocyanate has an amine equivalent of more than 300, a polyisocyanate monomer and / or a derivative of the polyisocyanate monomer may be appropriately added. , The amine equivalent is 140-300.
It may be adjusted so as to be within the range. When the amine equivalent of the modified polyisocyanate is in the range of 140 to 300, the modified polyisocyanate may be used alone as it is, or a polyisocyanate monomer and / or a derivative of a polyisocyanate monomer may be used in combination at an appropriate ratio. Is also good. Further, when the amine equivalent of the derivative of the polyisocyanate monomer is in the range of 140 to 300,
A derivative of the polyisocyanate monomer may be used as it is.

As such a polyisocyanate component having an amine equivalent of 140 to 300, an amine equivalent of 100
0.1 to 99 parts by weight, preferably 0.1 to 99 parts by weight of the modified polyisocyanate of 200 to 2,000, preferably 200 to 2,000.
5 to 90 parts by weight and an amine equivalent of 50 to 500, preferably 70 to 400, a polyisocyanate monomer and / or a derivative 1 of a polyisocyanate monomer.
It is preferable to use 99 parts by weight, preferably 5 to 95 parts by weight, and it is preferable that the polyisocyanate component contains a tri- or more functional polyisocyanate compound. Examples of the trifunctional or higher polyisocyanate compound include polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI)
And the like, and among the polynuclear bodies, those having three or more nuclei (trifunctional) are 1% by weight or more, and more preferably 5% or more.
Preferably, it is contained in an amount of at least% by weight.

If the amine equivalent of such a polyisocyanate component is less than 140, good sustainability of the effect cannot be obtained, and if the amine equivalent exceeds 300, the microbial growth inhibitor can be microencapsulated. However, again, good persistence of efficacy cannot be obtained.

The oily phase is, for example, based on 100 parts by weight of the organic solvent described above, and
Parts by weight, preferably 2 to 250 parts by weight, and based on a total of 100 parts by weight of the organic solvent and the microorganism growth inhibitor, 2 to 80 parts by weight of a polyisocyanate component having an amine equivalent of 140 to 300, preferably Can be obtained by blending 5 to 50 parts by weight.

The amount of the microbial growth inhibitor is not limited to the above range. In the obtained microcapsules containing the microbial growth inhibitor, the microencapsulated microbial growth inhibitor is effective. Any amount can be used as long as it can be expressed, and the amount varies depending on the type of the microbial growth inhibitor to be microencapsulated.

It is preferable that an acid chloride compound, an acid anhydride compound and / or an epoxy compound be blended in such an oil phase. By blending these, the oil phase can be stabilized. Examples of the acid chloride compound include benzoyl chloride, p-toluenesulfonic acid chloride, carbobenzoxychloride and the like. Further, as the acid anhydride compound,
For example, p-toluenesulfonic anhydride, tert-anhydride
-Butoxycarbonyl and the like. Examples of the epoxy compound include neopentyl glycol diglycidyl ether and ethylene glycol diglycidyl ether. These acid chloride compounds, acid anhydride compounds and / or epoxy compounds are preferably blended in an amount of 0.1 to 20 parts by weight, more preferably 0.3 to 10 parts by weight, based on 100 parts by weight of the organic solvent.

In the preparation of the oil phase described so far, an organic solvent may or may not be used. When an organic solvent is used, for example, a polyisocyanate component, a microbial growth inhibitor, and an acid chloride compound,
The acid anhydride compound and / or the epoxy compound may be mixed, stirred, and heated if necessary. The order of the compounding is not particularly limited, but if the polyisocyanate component has a relatively high viscosity, 40 to 1
It is preferable to heat to 50 ° C. Further, the used organic solvent may be removed, for example, by distillation.

The aqueous phase may be prepared, for example, by adding a dispersant to water. Examples of the dispersant include natural polysaccharides such as xanthan gum and arabic gum, for example, sodium carboxymethylcellulose,
Examples include semisynthetic polysaccharides such as methylcellulose and hydroxypropylcellulose, water-soluble synthetic polymers such as polyvinyl alcohol, anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. These dispersants may be used alone or in combination of two or more. The dispersant is used in an amount of 0.01 to 50 parts by weight, and more preferably 0.1 to 50 parts by weight based on 100 parts by weight of water.
It is preferable to mix in a proportion of 10 to 10 parts by weight.

To mix and disperse the oil phase and the aqueous phase prepared as described above, for example, an oil-in-water type (O / W type) in which the oil phase is dispersed as oil droplets in water of the aqueous phase ) Dispersion (emulsification) may be performed. More specifically, for example,
The oil phase may be added to water and stirred at room temperature with a mixer or the like until it becomes fine droplets.

Next, for interfacial polymerization after dispersion, the polyisocyanate component in the dispersed liquid may be reacted with an active hydrogen group-containing component. As the active hydrogen group-containing component, water in the aqueous phase may be used as it is, or the above-described active hydrogen group-containing compound may be used.

When the water in the aqueous phase is used as it is as the active hydrogen group-containing component, it may be continuously used after dispersion, for example, at 40 to 100 ° C., preferably 50 to 95 ° C.
Then, heating may be performed with stirring for 0.5 to 15 hours, preferably 1 to 8 hours. Thereby, a microcapsule in which the microbial growth inhibitor is encapsulated can be obtained by reacting the polyisocyanate component with water at the interface between the oil phase and the aqueous phase.

When an active hydrogen group-containing compound is used, the active hydrogen group-containing compound may be added to the dispersed liquid after the dispersion. More specifically, for example, as an aqueous solution of an active hydrogen group-containing compound,
It is preferable to drop the dispersion continuously after the dispersion. In order to make the active hydrogen group-containing compound an aqueous solution, the concentration is preferably not more than 50% by weight. For example, the active hydrogen group of the active hydrogen group-containing compound is converted to the isocyanate group of the polyisocyanate component. It is preferable to drop the solution to such an amount that the equivalent amount becomes almost equal. Also,
The active hydrogen group-containing compound to be added is preferably a low molecular weight polyamine, especially a polyamine having 2 to 12 carbon atoms, and more preferably a polyamine having 4 to 12 carbon atoms. Carbon number 2
Examples of the polyamines Nos. To 12 include ethylenediamine, 1,4-butanediamine, hexamethylenediamine, and octamethylenediamine. After the addition of the active hydrogen group-containing compound, the mixture is heated with stirring at 25 to 100 ° C, preferably 30 to 95 ° C, for 0.5 to 10 hours, preferably 1 to 7 hours to accelerate the reaction. Is preferred. Thereby, the microcapsules in which the microbial growth inhibitor is encapsulated can be obtained by reacting the polyisocyanate component with the active hydrogen group-containing compound at the interface between the oil phase and the aqueous phase.

Incidentally, such interfacial polymerization may be carried out by using water and an active hydrogen group-containing compound in combination depending on the purpose and use.

If necessary, known additives such as a thickener, an antifreezing agent, a preservative, a microbial growth inhibitor and a specific gravity regulator are added to the aqueous dispersion containing the microcapsules thus obtained. By appropriately mixing, the microcapsules containing the microorganism growth inhibitor of the present invention can be obtained. The microcapsules containing the microbial growth inhibitor of the present invention obtained as described above are in a state as they are (aqueous dispersant).
And after filtration, may be formulated into known dosage forms such as, for example, powders and granules, and used.

The microcapsules containing the microbial growth inhibitor of the present invention have excellent efficacy even when the microbial growth inhibitor as an active ingredient is well encapsulated and the amount of the microbial growth inhibitor used is small. It can be expressed, and the sustainability of its efficacy and sustained release can be sufficiently improved.

The coating composition of the present invention contains the microcapsules containing a microbial growth inhibitor thus obtained. The mixing ratio of the microcapsules containing the microbial growth inhibitor in the coating composition is 0.005 to 10% by weight, preferably 0.01% by weight, as the microbial growth inhibitor.
~ 5% by weight. Further, the coating composition of the present invention contains a composition required as a coating, for example, a resin, and if necessary, an extender pigment, a coloring pigment, and other additives.

Examples of the resin include, but are not limited to, acrylic resins, acrylic styrene resins, styrene resins, vinyl chloride resins, vinyl acetate resins, vinyl acetal resins, fluororesins, polyester resins, and the like.
Amino resin, epoxy resin, polyurethane resin, silicone resin and the like are used. Among these, an acrylic resin is preferably used. The mixing ratio of the resin in the coating composition is 5 to 99% by weight, preferably 10 to 80% by weight. These resins are preferably emulsion resins as described later, and as the emulsion resin, an acrylic emulsion resin is preferably used.

As the extender, for example, calcium carbonate, talc, clay, barium sulfate, silica, calcium carbonate and the like are used. This extender pigment may not be particularly blended, but when it is blended, the blending ratio of the extender pigment in the coating composition is 0.1 to 50% by weight, preferably 1 to 30% by weight.

As the coloring pigment, for example, inorganic pigments such as titanium white, red iron oxide, chromium oxide, graphite and zinc oxide, and organic pigments such as Hansa Yellow, Lake Red, Phthalocyanine Blue and Shinkasha Red are used. This coloring pigment does not have to be particularly blended, but when it is blended, the blending ratio of the coloring pigment in the coating composition is 0.1%.
It is from 0.01 to 50% by weight, preferably from 1 to 30% by weight.

As other additives, various additives such as an antioxidant, an ultraviolet absorber, a preservative, a fungicide, an antialgal agent and an antibacterial agent are used. It is appropriately blended depending on the conditions.

The form of the coating composition of the present invention is not particularly limited.
Further, it can be used as a water-based coating composition.
When used as an organic solvent-based coating composition, the components including the microbial growth inhibitor-containing microcapsules described above may be prepared by dispersing in an organic solvent in an appropriate ratio. When used as a composition, the components may be prepared by suspending or emulsifying each component including the microbial growth inhibitor-containing microcapsules in water at an appropriate ratio by suspension or emulsification.

Of these, the coating composition of the present invention is preferably prepared as an aqueous coating composition. If prepared as a water-based coating composition, it can be obtained as a coating composition that is friendly to the global environment. Above all, zero VOC
When incorporated into a paint, it is environmentally friendly and can maintain the stability of the microbial growth inhibitor-containing microcapsules in a favorable manner, thereby further improving the sustainability of the efficacy and the sustained release.

To prepare the coating composition of the present invention as a water-based coating composition, for example, an emulsion coating, for example, after preparing a mill base containing an extender pigment and a coloring pigment, the mill base is added to the mill base as a letdown. Each component is blended sequentially. Mill base is prepared by, for example, mixing water with an extender or a coloring pigment, and adding known additives such as an antifreezing agent (such as ethylene glycol), a dispersant, a wetting agent, and an antifoaming agent, if necessary. Mix and stir. Then, on the mill base prepared in this manner, microcapsules containing an emulsion resin and a microbial growth inhibitor as a letdown, if necessary, a surfactant, a film-forming auxiliary (such as a high boiling point solvent), and an antifoaming agent. After adding known additives such as a pH adjuster and a thickener, the mixture may be stirred and mixed.

The coating composition of the present invention contains a microbial growth inhibitor-containing microcapsule in which the microbial growth inhibitor, which is an active ingredient, is well encapsulated. Even if the amount is small, an excellent effect is exhibited and the effect is maintained by the improved sustained release of the microorganism growth inhibitor.

When the microbial growth inhibitor is blended as such a microcapsule containing a microbial growth inhibitor, a favorable working environment can be ensured when blended into the coating composition, and at the same time, It does not cause crystallization and deterioration of paint quality or microbial trouble,
It can be used effectively as a stable quality coating composition without discoloration after compounding.

Therefore, the coating composition of the present invention can be widely applied to various industrial products requiring durability, and more specifically, is suitable for indoor and outdoor coating applications of civil engineering and building structures. Can be applied to Also, for example,
It is prepared as a clear paint without blending coloring pigments and extender pigments, and is used for paper and synthetic resins such as wallpaper, wood such as decorative boards and synthetic boards, inorganic base materials such as cement and concrete, ceiling materials and wall materials, etc. It may be used as a coating composition for boards.

[0052]

The present invention will be described more specifically with reference to the following examples and comparative examples.

Production Example 1 (Production of Microcapsule Aqueous Dispersant (1)) 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide (hereinafter, referred to as slab curve)
After dissolving 7 g in 33 g of Allosizer 202 (ethyl biphenyl, boiling point: 286 ° C., manufactured by Nippon Steel Chemical Co., Ltd.), the solution was heated to 60 ° C., and takenate which was previously dissolved at 80 ° C. L-5060 (ε-caprolactone-modified polyisocyanate of diphenylmethane-4,4′-diisocyanate (hereinafter referred to as MDI): amine equivalent 670, manufactured by Takeda Pharmaceutical Co., Ltd.) 1.3
5 g and 3.15 g of Millionate MR200S (polymethylene polyphenyl polyisocyanate: amine equivalent 132 (50% by weight or more of trinuclear or higher polynuclear), manufactured by Nippon Polyurethane Industry Co., Ltd.) are mixed and dissolved.
An oil phase was prepared.

On the other hand, in 50 g of water, 9 g of a 5% by weight aqueous solution of polyvinyl alcohol (Poval 217, manufactured by Kuraray Co., Ltd.), 9 g of a 2% by weight aqueous solution of sodium carboxymethylcellulose, and 20% by weight of Demol NL (anionic surfactant) An aqueous phase was prepared by mixing 4 g of an aqueous solution (manufactured by Kao Corporation) at room temperature.

Next, the oil phase was added to the aqueous phase. K. The mixture was dispersed by stirring with an auto homomixer for several minutes. The rotation speed of the mixer at this time was 5000 min.
^-1 . Then, during this stirring, 5 g of an aqueous solution containing 1.50 g of hexamethylenediamine was dropped. Then, the obtained aqueous dispersion was reacted in a constant temperature bath at 75 ° C. for 3 hours while gently stirring to obtain an aqueous dispersion containing microcapsules enclosing a slab curve. After adjusting the pH to 7 with a 0.1N hydrochloric acid aqueous solution and a 0.1N sodium hydroxide aqueous solution, pure water was added to obtain a microcapsule aqueous dispersant (1) having a slab curve content of 5% by weight.

Production Example 2 (Production of Microcapsule Aqueous Dispersant (2)) Microcapsules having a slab curve content of 5% by weight were prepared in the same manner as in Production Example 1, except that the amounts of the components shown below were changed. Water dispersant (2) was obtained.

Takenate L-5060 2.38 g Millionate MR200S 2.38 g Hexamethylenediamine 1.24 g Production Example 3 (Production of microcapsule aqueous dispersant (3)) 6 g of OIT and 6 g of IPBC were added to Allosizer 202
After dissolving in 8 g, the solution was heated to 60 ° C., and Takenate L-5 previously dissolved at 80 ° C. was added thereto.
060 0.52 g and Millionate MR200S
An oil phase was prepared by mixing and dissolving 65 g.

On the other hand, an aqueous phase was prepared by mixing 50 g of water with 9 g of a 5 wt% aqueous solution of polyvinyl alcohol, 9 g of a 2 wt% aqueous solution of sodium carboxymethyl cellulose, and 4 g of a 20 wt% aqueous solution of Demol NL at room temperature.

Next, the oil phase was added to the aqueous phase. K. The mixture was dispersed by stirring with an auto homomixer for several minutes. The rotation speed of the mixer at this time was 5000 min.
^-1 . Then, during this stirring, 5 g of an aqueous solution containing 0.83 g of ethylenediamine was dropped. Next, the obtained aqueous dispersion was reacted in a constant temperature bath at 75 ° C. for 3 hours with gentle stirring to obtain an aqueous dispersion containing microcapsules in which OIT and IPBC were encapsulated. To this, 0.1N hydrochloric acid aqueous solution was added to adjust the pH to 7, then pure water was added, and the OIT-IPBC content was 5 wt%.
To obtain a microcapsule aqueous dispersant (3).

Production Example 4 (Production of Microcapsule Aqueous Dispersant (4)) Except that the amounts of the components shown below were changed, the same operation as in Production Example 3 was carried out to reduce the OIT-IPBC content to 5% by weight. A microcapsule aqueous dispersant (4) was obtained.

Takenate L-5060 0.70 g Millionate MR200S 3.96 g Ethylenediamine 1.34 g Production Example 5 (Production of microcapsule aqueous dispersant (5)) Except that the amount of each component shown below was changed, Production Example By the same operation as in 3, microcapsule aqueous dispersant (5) having an OIT-IPBC content of 5% by weight was obtained.

Takenate L-5060 0.35 g Millionate MR200S 1.98 g Ethylenediamine 0.67 g Production Example 6 (Production of microcapsule aqueous dispersant (6)) Except that the amount of each component shown below was changed, Production Example By the same operation as in 3, microcapsule aqueous dispersant (6) having an OIT-IPBC content of 5% by weight was obtained.

1.25 g Takenate L-5060 1.25 g Millionate MR200S 1.25 g Ethylenediamine 0.50 g Comparative Production Example 1 (Production of Microcapsule Aqueous Dispersant (7)) Instead of 1.35 g Takenate L-5060 and 3.15 g Millionate MR200S , Millionate M
The same procedure as in Production Example 1 was carried out except that 4.20 g of R200S was used, and 1.80 g of hexamethylenediamine was used instead of 1.50 g of hexamethylenediamine. Powder (7) was obtained.

Comparative Production Example 2 (Production of Microcapsule Aqueous Dispersant (8)) MDI 4.2 was used in place of 1.35 g of Takenate L-5060 and 3.15 g of Millionate MR200S.
0 g, and 1.50 g of hexamethylenediamine
In place of the above, 1.80 g of hexamethylenediamine was used, and the same operation as in Production Example 1 was performed to obtain a microcapsule aqueous dispersant (8) having a slab curve content of 5% by weight.

Comparative Production Example 3 (Production of Microcapsule Aqueous Dispersant (9)) 6 g of OIT and 6 g of IPBC were added to Allosizer 202 2
After dissolving in 8 g, the solution was heated to 60 ° C., and mixed with millionate MR2 previously dissolved at 80 ° C.
An oil phase was prepared by mixing and dissolving 10.2 g of 00S.

On the other hand, 4.5 g of a 5% by weight aqueous solution of polyvinyl alcohol, 4.5 g of a 2% by weight aqueous solution of sodium carboxymethylcellulose, and 2 g of a 20% by weight aqueous solution of Demol NL were mixed at room temperature with 35 g of water.
An aqueous phase was prepared.

Next, the oil phase was added to the aqueous phase. K. The mixture was dispersed by stirring with an auto homomixer for several minutes. The rotation speed of the mixer at this time was 5000 min.
^-1 . During the stirring, 5 g of an aqueous solution containing 1.8 g of ethylenediamine was dropped. Then, the resulting aqueous dispersion was reacted in a constant temperature bath at 75 ° C. for 3 hours with gentle stirring to obtain OIT and IIT.
An aqueous dispersion containing microcapsules encapsulating PBC was obtained. A 0.1N aqueous hydrochloric acid solution was added thereto to adjust the pH to 7, and then pure water was added to obtain a microcapsule aqueous dispersant (9) having an OIT-IPBC content of 5% by weight.

Comparative Production Example 4 (Production of Microcapsule Aqueous Dispersant (10)) 6 g of OIT and 6 g of IPBC were added to Allosizer 202 8
g, the solution was heated to 60 ° C. and mixed with millionate MR2 previously dissolved at 80 ° C.
An oil phase was prepared by mixing and dissolving 5.1 g of 00S.

On the other hand, 9 g of a 5 wt% aqueous solution of polyvinyl alcohol, 9 g of a 2 wt% aqueous solution of sodium carboxymethyl cellulose, and 4 g of a 20 wt% aqueous solution of Demol NL were mixed at room temperature with 50 g of water to prepare an aqueous phase.

Next, the oil phase was added to the water phase, and T.P. K. The mixture was dispersed by stirring with an auto homomixer for several minutes. The rotation speed of the mixer at this time was 5000 min.
^-1 . During the stirring, 5 g of an aqueous solution containing 0.9 g of ethylenediamine was dropped. Then, the resulting aqueous dispersion was reacted in a constant temperature bath at 75 ° C. for 3 hours with gentle stirring to obtain OIT and IIT.
An aqueous dispersion containing microcapsules encapsulating PBC was obtained. A 0.1N aqueous hydrochloric acid solution was added thereto to adjust the pH to 7, and then pure water was added to obtain a microcapsule aqueous dispersant (10) having an OIT-IPBC content of 5% by weight.

Comparative Production Example 5 (Production of Liquid Preparation (11)) 5 g of OIT and 5 g of IPBC were added to methyl carbitol 9
The solution (11) was obtained by dissolving in 0 g.

The formulations of Production Examples 1 to 6 and Comparative Production Examples 1 to 5 are shown in Table 1.

[0073]

[Table 1] Examples 1 to 6 and Comparative Examples 1 to 6 In the proportions (% by weight) shown in Table 2, first, titanium white was added to water, and further, ethylene glycol, a dispersant, a wetting agent, and an antifoaming agent were added. A mill base was prepared by stirring and mixing. Next, as a letdown, an emulsion resin, a film-forming aid, an antifoaming agent, and an active ingredient (microcapsule aqueous dispersants (1) to (10), liquid (11), or aqueous suspension (12)) (Methyl-2-benzimidazole carbamate 10% by weight aqueous suspension, coatside D, manufactured by Takeda Pharmaceutical Co., Ltd.)), a thickener, and water were sequentially added, followed by stirring and mixing to obtain Example 1.
To 6 and Comparative Examples 1 to 6 were obtained. Details of each component are shown below. In addition, at the time of the preparation, the coating compositions of Examples 1 to 6 can be prepared in a good working environment without skin irritation, and can be mixed well without causing crystallization. Was.

(Mill base) Titanium white: rutile type titanium oxide (trade name: TITANI)
X JR-900, manufactured by Teika Co., Ltd.) Dispersant: sodium polycarboxylate (trade name: Orotan 850, manufactured by Rohm and Haas) Wetting agent: alkyl ether sulfate (trade name: Triton CF-10, (Union Carbide Co., Ltd.) Antifoaming agent: Mixture of mineral oil and polyethylene glycol type nonionic surfactant (trade name: Nopco 8043-L, manufactured by San Nopco Co., Ltd.) (Letdown) Emulsion resin: Acrylic / styrene type Emulsion resin (trade name: Ultrasol C-62, manufactured by Ganz Chemical Co., Ltd., solid content: 55% by weight) Film-forming aid: 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate ( Trade name: CS-12, manufactured by Chisso Corporation) Antifoaming agent: Mixture of mineral oil and polyethylene glycol type nonionic surfactant Product surface: Nopco 8034-L, manufactured by San Nopco Limited) thickener: urethane modified polyether thickener (trade name:
RM-8W, manufactured by Rohm and Haas)

[0075]

[Table 2] Test Example 1 (mold resistance) A mold resistance test was performed using each of the coating compositions obtained in Examples 3 to 6 and Comparative Examples 3 to 6. The fungicide test is
The following procedure was used.

As the test mold liquid, Aspergillus niger, Penicillium citrinum (Pe
nicillium citrinum) and a mixture of Cladosporium cladosporioides.

No. (5) A coating composition having the same weight as that of the filter paper was uniformly applied on the filter paper and dried to prepare a coating sample. Using the obtained coating sample, the antifungal effect was evaluated by the following test method.

1) Test method (1) A coated sample was cut into a size of 30 × 30 mm, and this was used as a test piece and naturally dried for 24 hours.

(2) The test piece was immersed in 200 mL of water at 40 ° C. for 6 days and air-dried for 24 hours.

(3) A glucose agar medium sterilized by an autoclave was poured into a petri dish having a diameter of 9 cm, and a test piece was stuck on the center of the solidified agar plate.

(4) The test mold solution was sprayed on a test piece, and then cultured at 28 ° C.

(5) Four weeks later, (3) and (4) were repeated.

(6) Four weeks after the culture, the degree of mold growth on the test piece was determined. The criteria are as follows. Table 3 shows the results.

2) Judgment criteria-: No mold growth was observed on the test piece.

±: Very little mold growth was observed on the test piece.

+: Mold growth was observed on 1/3 or less of the test piece.

++: Mold growth was observed on 2/3 or less of the test piece.

+++: More than 2/3 mold growth on the test piece was observed.

[0089]

[Table 3] Test Example 2 (Stability) After the coating compositions obtained in Example 4 and Comparative Example 5 were left in a sealed state at 60 ° C. for 2 weeks, the residual ratio of the active ingredient in the coating compositions was determined by liquid chromatography. I asked. Table 4 shows the results. In addition, the coating composition of Example 4
Even after being left for two weeks, good properties were maintained without discoloration.

[0090]

[Table 4] Test Example 3 (Preservation) A preservation test was performed using each of the coating compositions obtained in Examples 1 and 2 and Comparative Examples 1 and 2. The preservative test was performed according to the following procedure.

[0091] The pre-precultured bacterial count known rot species, was added to a 10 ^three in each coating composition, at 33 ° C., after a predetermined number of days culture shown in Table 5, agar pour plate method Was measured. Table 5 shows the results.

[0092]

[Table 5] Test Example 4 (Crystallinity) The coating compositions obtained in Example 4 and Comparative Example 5 were left in a sealed state at -5 ° C for 2 weeks, diluted 5 times with water (5 ° C), and observed under a microscope. Observed. As a result, in the coating composition of Example 4, no precipitate such as needle-like crystals was observed, whereas in the coating composition of Comparative Example 5, needle-like crystals were observed.

[0093] In Tables 1 to 5, "-" in the column other than the fungicide resistance indicates the case where no compounding was performed or the case where no measurement was performed.

[0094]

As described above, the coating composition of the present invention contains a microbial growth inhibitor-containing microcapsule in which the microbial growth inhibitor, which is an active ingredient, is well encapsulated. Even if the amount of the growth inhibitor used is small, excellent efficacy is exhibited, and sustainability of the efficacy and sustained release can be sufficiently improved.

When the microbial growth inhibitor is blended as such a microcapsule containing a microbial growth inhibitor, a favorable working environment can be ensured when blended with the coating composition, and at the same time, It can be effectively used as a stable quality coating composition without causing crystallization or discoloration after compounding.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A01N 47/12 A01N 47/12 Z B01J 13/16 C09D 5/02 C09D 5/02 5/14 5/14 7/12 7/12 B01J 13/02 DF term (reference) 4G005 AA01 AB14 BA02 BB06 BB12 DA05W DA12W DA13W DB05W DB13W DB16W DC42Y DC46Y DC51X DC54X DC61X DD04Z DD08Z DD38Z DD39Z DD57Y EA03 4H011 AA02 BB03 DH02 DH05 DH10 DH25 4J038 CC021 CD021 CD091 CE061 CF021 CG001 DA111 DB001 DD001 DG001 DG052 DG062 DG102 DG112 DG122 DG192 DG292 DL031 HA156 JA31 JB10 PC18 JB18 PCB

Claims (5)

[Claims] 1. The method according to claim 1, wherein the microorganism growth inhibitor has an amine equivalent of 140.
A coating composition comprising microcapsules containing a microbial growth inhibitor microcapsulated by a film formed by the reaction of the polyisocyanate component with an active hydrogen group-containing component. 2. The coating composition according to claim 1, wherein the polyisocyanate component having an amine equivalent of 140 to 300 contains a polyisocyanate compound having three or more functional groups. 3. The coating composition according to claim 1, wherein the active hydrogen group-containing component is water and / or a polyamine having 2 to 12 carbon atoms. 4. The microbial growth inhibitor comprises at least one active ingredient selected from the group consisting of a thiophene compound, an isothiazoline compound and an organic iodine compound. 4. The coating composition according to any one of 3. 5. The coating composition according to claim 1, wherein the coating composition is an aqueous coating composition.